Coordination polymer (CP) glasses have recently emerged as a new glass state. Given the young state of the field, the discovery of concepts that guide the synthesis of CP glasses with targeted thermal and macroscopic properties is at the center of ongoing research. In our work, we draw inspiration from research on inorganic glasses, investigating the impact of Li(C2N3) as a modifier on the thermal properties of the new molecular perovskite [(C3H7)3N(C4H9)]Mn(C2N3)3 (with [C2N3]− = dicyanamide, DCA). We derive the phase diagram and show that Li(C2N3) and [(C3H7)3N(C4H9)]Mn(C2N3)3 form a eutectic mixture, in which the melting temperature is decreased by 30 K. Additionally, for the eutectic mixture at xLiDCA ≈ 0.4, a CP glass forms under slow cooling, opening interesting pathways for scalable synthesis routes of CP glasses. Given the virtually unlimited parameter space of hybrid modifiers, they will play a major role in the future to alter the glass’ properties where the availability of rigorously derived phase diagrams will be important to identify material class overarching trends.
